Art of cracking hydrocarbons



May 22,1945.k J, w- TETER 2,376,833

ART 0F CRACKING HYDROCARBONS Filed Feb. 19, 1941 v (.Mllmmwh a ATTORNEYS Patented Mey 2 2, 1945 UNITED STATE s PATENT OFFICE escasas' am' or casema' nvnnocannons y Rening Company,

ration of Maine Jenn w. 'recel-,omessa nl., einer te einem:

New vYork, N. Y., 4a corpo- Appueeuon February 19,1941, serial No. 379,594 "s claims. (ci. 19a-s2) My present invention relates, to improvements in the production of motor fuel gasoline of high anti-knock value by conversion of higher boiling hydrocarbons, or hydrocarbons of the same general boiling range but of lower anti-knock value,

processin which the production of gasoline per unit of catalyst per unit of time can be limited without corresponding limitation of total .gasoline inducedvby `contact with a catalyst at elevated A temperature. The general objects of my invention include, in processes for such production of motor fuel gasoline, improvements in elciency and economy, improvements in yield and Particularly in reduced production of normally incondensible gases, and improvements in the antiknock value of the product.

In thermal conversion processes in which catalis not such as to involve changes in the reactions characteristic of the conversion. In thermal conversion processes involving catalysis, -temperature. time and pressure are also controlling factors, but therelationship does not appear to be the same, particularly when related to qualitiesl of the product such as anti-knock value.

I have found that a minimum period of contact between hydrocarbons and catalyst under conversion conditionsv is required to secure high yields of a motor fuel gasoline product of high antiknock velue with low gas production, that the production of gasoline per unit of catalyst per ,unit of time should be limited to maintain production of a product of high anti-knock value, and that increasing the apparent period of catalyst contact by increasing the lpressure does not have the same eifect as otherwise increasing the period of catalyst contact at the same pressure. The process of my present invention embodies one application of these discoveries. More particularly, the objects of my invention include the provision of a process in which catalyst contact -is cyclically maintained within the system, of a process in which catalyst contact is,- satisfactorily maintained for an appropriate minimum period, of a process in which catalyst contact is maintained without requiring substantial pressure increases in the region of catalyst contact, of a production per unit of catalyst or per unit oftime@ and of process in which substantially optimum conditions for the desired conversion can be maintained throughout the region of catalyst contact;

In the process `of my invention a charge 'of hydrocarbons Asubstzatntially in vapor phase is maintained in'a cycle of movement in a closed stream, hydrocarbons to be processed and a conversion catalyst are introduced into this stream,

the catalyst is maintained in suspension in the circulating stream of hydrocarbons by the velocity of movement in the cycle, a part of the stream of hydrocarbons and suspended catalyst is4 dis` 'charged from the cycle, and spent catalyst and a gasoline fraction are separated from the dis- .charged part. The cyclically circulating stream of hydrocarbons andsuspended catalyst is maintained at a temperature and under a pressure for a period of .time appropriate'to effect the conversion. The temperature is ofthe order of 950- 1050 F. A temperature of 1025"-,1050 IF'.` is an approximate optimum for many stocks. At temperatures much below about 950 F. the reaction i.

rate begins to fall without any corresponding advantage in terms of the anti-knock value of the product. As the temperature approaches about l 10501100 F., the gas production begins to increase without any corresponding advantage, and sometimes with actual loss, in terms of the anti, knock value of the product unless high ratios of catalyst to hydrocarbons to be processed are used. The pressure is of an order low enough to permit vaporization of the hydrocarbons to be processed at the temperature used. In general the pressure should not exceed about 100 pounds per square inch;` usually a pressure oi the order of 30-'15 pounds per square inch is advantageous. The conversion temperature used is with advantage maintained lsubstantially uniform throughout the cycle. The rate of introduction of hydrocarbons to be procsed and the conversion catalyst and the rateofv discharge of hydrocarbons and suspended catalyst from the cycle correspond and are regulated to maintain the hydrocarbons to be processed within the cycle for a minimum period of about 15- -25 seconds. With appropriate catalyst: hydrocarbons ratios, 'depending upon the v.ji'activ'ity of .the catalyst, the average processing time in 'the cycle need not substantially exceed this minimum, although much longer Deriodsare K throughout thercy'cle.

-andregulatedmymeans of valve Il. The discharge pressure from l, for esample,

emessa t useful in carrying out my invention. For example, the period may be as much as 200 or 300 seconds or more. Usually, optimum resultsare to be secured with a period of the order of 30`90 V seconds. With fuilers earth as the'conversion catalyst,4 for example, a catalyst:hydrocarbons ratio'by4 .weight of from 202100 to 100:100 or may approximate 20o-600 pounds .per square inch. Substantially all or part of such pressure somewhat higher may be used forvexample. The

t process of my invention is appropriately applied with the known conversion catalysts generally. -With more active conversion catalysts, the cataiystzhydrocarbons ratio is with advantage usually reduced in more or less general correspondence with the increase in activity of the catalyst as compared to the ratioslindicated as useful with fullers earth. The conversion catalyst should be reduction' upon discharge from the heater Imay also'be effected during flowv through the Jetpipe I0. The conversion catalyst, fuller-s earth of 200v forced into the ljet Il and is carried' through the jetpipe'and introducedinto the re mesh .or ilnerjfor example, is-

pipe I through connection action chamber by the stream of .hydrocarbons discharged .from the heater I The conversion catalyst lmay be forced into the jet pipe as a reduced to a nne state of subdivision beforeuse.

for example to 200 mesh or nner, to facilitate its suspension by the velocityfof movement of the hydrocarbon vapors in the cycle of my process. The movement of the hydrocarbon-lvapors in the cycle is with advantage maintained by injecting the hydrocarbons to be processed into the `circulatingl stream of hydrocarbons as ajet. Circulation of the ,hydrocarbons is thus maintained and suspension. of the catalyst is thus promoted and maintained in a particularly .advantageous manner.- A plurality ofsuch jets may be introduced at a number'of points in the cycle to assist in the maintenance of uniform conditions slurry, in a hydrocarbon oil corresponding tothe stock to be processedv for'exa'mple, or it may be forced into the jet pipe Illas a pulverulent'solid by means `of appropriate feeding mechanism, for

' example as describedV in my application Serial No. 339,458, filed June 8, 19-i0. ljThe catalystzhydrocarbons ratio is fixed by, proportioningthe v charging rates of the stock to beprocessedand the conversion catalyst.

The heater Imay be of any conventional type.- I

As illustrated it is of the' type described in Letters Patent No. 1,717,334, granted June 1.1, v1929.

The process 'o'f .my invention will,be further described irl-connection with theaccompanying drawing which illustrates, A diagrammatically and conventionally, .in elevation and partly in section and with partsbr'oken away, one form of apparatus appropriate for carrying out the process. r

The apparatus illustrated in the drawing comprises a heater I, a reaction chamber 2, a separator l, a fractionating tower l, a condenser 5 and a receiver 6. Hydrocarbon bi1 to be processed, supplied through connection 'I, is forced, by means ofpump 8, through the heater I- and.

through connection 9 and. jetjppe III, into the reaction chamber 2'. The conversion catalyst-lis' forced into the reaction chamber 2Y through connection II `and jet pipe I Il. mdrocarbons and suspended catalyst are discharged from the reaction chamber 2 through connection I2 into separator 3. Spent catalyst isdischarged from the separator 3 through connection I3. 'Ihehydrocarbons pass through connectiony I4 to the lower end of the fractionating tower l.A Ajheavy .fraction and an intermediate fraction separated inthe fractionating tower are discharged through connections I5 and I6, respectively, and a gaso lin'e fraction, separated as an overhead vapor fraction, passes to the receiver 8 through connection I1 and condenser l.

The stock to .be processed, a 'gas' oil fraction for example, is brought, in the heater I, to a temperature, measured as it enters the jet pipe I0,

approximating 100W-10.50 F. or somewhat higher. l This heating is with advantage carried out at rate so high'that cracking in' the heater I is kept at a minimum asa rult of limitation of the-time :factorL The heater I maybe1operated just sumcient to effect discharge' ofV thel into the reaction lthe heater. I iswithadvantage opa-ated under a substantially higher pressure than "that, maintained in the reaction being reduced on an application of Lus'de Florez, arranged for downdraft operation. With this type of furnacev the heating coils are with advantage divided into two or more banksl of series connectedA heating tubes,v the several banks being connected inpatallel.

In the reaction chamber 2, the hydrocarbons are maintained atfa conversion temperature and under a conversion pressure` 'while contact between the catalyst and the hydrocarbons is cyclically maintained, these conversion conditions and the catalyst suspension being -maintained sub stantially uniform by the velocity of movementA phase, although some unvaporized oil may 'be present as a mist or fog and although some condensation of hydrocarbons may take place upon the suspended catalyst particles.

action chamber 2 may be supplied as Sensible heat of the hydrocarbons introduced through jet .pipe I0, the reaction chamber 2 lbeing thermally v insulated to maintain the temperature, or, land usually with advantage, this heat may be supplemented for example by mild external heating of the reaction chamber` 2, by circulatingl heating gases through an oven 20 in which the reaction chamber is arranged, as in the apparatus illustrated for example. `To maintain uniform temperature conditions in such an oven, a `large part, for example as muchas 90%,vof the heating gases leaving the oven may be recirculated there.-

through together with a correspondingly smallA part of makeup hotproducts of combustion from an' appropriate furnace. The heating of the heater I and the reaction chamber 2 may with` advantage' be) carried out inthe general manner described for heating the heating coils and the reaction chambers in Letters' Patent No.' 1,949,655,

The heat to' maintain` the conversion temperature in the re-v mma miren 1934. on sa' stpucsugt or L. Pelzer. As previously indicated, two or more Eugene C. Herthel.`

Jet pipes and cooperating constrictions.- Il andv il,

'may be arranged at' spaced Points along the cyclic path of travel through the reactionchamber. al-

though' but asinglejet pipe'and constriction is illustratedin the accompanying drawing. Also.

a plurality of reaction chambers arranged as de-` scribed may be operatedin parallel. l In the separator I, maintained` at high tein-- perature by 'appropriate thermal insulation, the

l from the overhead fraction discharged from tower 'i through connection il is discharged 'from receiver e throu'ghconnection and-the mixture ot gases and vapors remaining unconexam'ple inappropriate apparatus for vthe rjecov eryof .condensible hydrocarbonl components` of bulk oi the suspended catalyst is separated, again by the' iamiliar cyclone eirect, from'that-part ol the' hydrocarbon-catalyst mixture discharged from the reaction chamber! through connection I2. The separated lspent catalylti -through an appropriate seal, l such as-a f'star" mechanism,.for regeneration or other disposal.

The remaining vapor mixture oi' hydrocarbons containing a small proportion of suspended catalyst is discharged into the iractionating tower I through connection M.'-

The tractionating towerisin edect two iracvtionatlng towers divided by-the'plateli.' In th'e lower 'part a heavy fraction in the form Vof a ta-i'-l --stantiallyuniform 'conditions throughout the lyst contact-fOr lllaillta'irihigy this Velocity 0f ,Y or catalyst contact. and` particularly th'e mini-' 2liA containing the catalyst remaining' in suspension charge'd through connection Il. To facilitate this Aseparation-and to promote lcleanliness of vapor mixture leaving the lower partei-the tower.

a number. of openvbaiiies 'followed by one or more "bubble" trays are arranged above the point of entrance of connection il and below the plate v2| and a renuxing medium, serving also as a wash r after the hydrocarbons'havefpassed throush the separator I is condensed and separated and 'discatalyst contact is cyclically maintained in the 'reaction chamber by the v velocity of now-oi hydrocarbons maintained in' the. cycleV loi' movement 'within the reaction' chamber.l 'The velocity in this same cycle of movement also maintains subregion ci catalyst 'contact thus permlttingthe vmainten of substantially optimum conversion condition' through' this region. I'urtherrmechanical working parts exposedto the, hydrocarbons and to the catalystin the region oi' catmovement are rendi'ered'unnecessary. The period mum perlod,- is easily controlled 'and is' easily maintained within' the stated limits, and this is accomplished4 without requiring substantial presj sure increases, for exam ple such as might be involved in the pressure drop through a long singlehigh enough to maintain. catalyst suspension.

' Similarly. the production of gasoline per unit oi oil, 'is introduced' over'one or more of these trays or b'aiiies.- For examplefa reduced crude'petroleum containing fa ga's oil stock appropriate to be I vsupplied to thel heater i may Ibe-;.introduced through either or both connections 2l and-2l, the

gas oil stock being vapcrised from 'the crude to Y escape from the lower part oi' the tower with the" `lower-'boiling vapors iromfthe separator 3 and vthe consequentcooling and washing of the vapors in the lowerl part oi' the tower servingto separate a tar containing thejsmall proportion of suspendedl catalyst remaining; in' the vapors from theseparator I.A The temperature of the vapor mixture passing through the plate 2|- may approximate 650-775 F. i'or example under a pressure at this point of about 20-30 inch.4 In the upper part oi' the tower l, a Zasoline fraction or a fraction containing a .substantial proportion oi.' gasoline is separated from a higher boilingv fraction, the latter being discharged through connection il fromabove plate Ii.- This intermediate fraction maybe supplied through connection 'I to heater I and may constitute all or part of the stock supplied to the heater. Frac- A tionation in the upper part oi' the tower may be pounds per square catalystper passage through the cycle in there- 'aetion'chamber can be limited to produce a prod'- uct ot high anti-knock value without involving losses in catalyst separation and reheating. ofthe' hydrocarbons which would be involved 'but for the cyclic characterro'f the process oi' my invention.

In this manner -my process aii'onfs improvements in emciency and economy, 'improvements in yield and'iinprovemen'ts in the anti-knock value ofthe v l therethrough by the velocity oimovement in the controlled by the direct'fintroduction of av reiiux- I ing medium, for example a part ofthe condensate v separated in the receiver I, through'conn'ection 24 or by circulation of a'copling or heat exchange medium through dephlegmator liwor by these means 4jointly.' The temperature of the vapor l mixture leaving the upper end ot tower I may approximate 365-385 F. The lower and upper parts of the fractionatingtower i may with advantage be operated in the manner described' for the nrst and second fractionatlng-towers (l and i2), respectively, in Letters Patent No. 1,810,048, granted June 16, 1931', on an. application of cycle, maintaining said circulating stream'oi hy-` drocarbons and suspended catalyst at a tempera-- ture of the order of 950-l050 1". vunder a pressure not 'exceeding about 100 pounds per square inch for a minimum-period of. about iii-2li seconds. discharsina part of said stream oi hydrocarbons and suspended catalyst, and separating spent catalyst and a gasoline fraction from that discharged part.

' Y2. In the production-of gasoline. 'the improvement which comprises maintaining a charge oi hydrocarbons substantially in vaporphasein a rapidly moving. substantially'uniform of movement in a closed stream by injecting hydro.' carbons to be processed into said stream aa a Jet. f

introducinfa conversion catalyst into stream, maintaining the catalyst in in the circulating stream of hydrocarbons and sub- `stantially uniformly distributed therethrough by. the velocityiot' movement in the cycle, maintaining said circulating stream of hydrocarbons and IiDwded catalyst 'at a ofthe'order gasolinefraction in condenser densed isdischarged through connection Il, vfor In carrying out the''process'of invention,

pass tube" with' a rateotilowthroughthe 'tube 'period ofabom 15-25 discharging Y v and AsuspendedY um apentoatalysltl-:lntcl asas oline traction from that 13'. in the productionofsasollnelthe improvement 'thick-comprises maintaining a charge yof -hydrocarbom 'substantially in vapor phase in a rapidlymoving uhstantially uniform cycle; of movement in a introducing hydrocarbon: to be processed-and a conversion catalyst apart" 'arranca bons *Immune therethrough by the velocity of movement inthe cyclelmaintaining and circulating mem may,

drocarbons, and suspende'dcatalyst at -a temperature substantially uniform throughput the vcycle Sure not exceeding aboutf1f00' pounds per sduare inch :or a minimum -periodfof about 15V-'25 seconda, discharging@ of, said stream of hydrocarbons-and suspended catalyst, and separating spent cata1ys t-and a".gasoline `function from that 

